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EP1074369A1 - Verfahren zur Herstellung von hochbeanspruchten Verbundteilen - Google Patents

Verfahren zur Herstellung von hochbeanspruchten Verbundteilen Download PDF

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Publication number
EP1074369A1
EP1074369A1 EP00115999A EP00115999A EP1074369A1 EP 1074369 A1 EP1074369 A1 EP 1074369A1 EP 00115999 A EP00115999 A EP 00115999A EP 00115999 A EP00115999 A EP 00115999A EP 1074369 A1 EP1074369 A1 EP 1074369A1
Authority
EP
European Patent Office
Prior art keywords
fibers
precomposite
composition
resin
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00115999A
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English (en)
French (fr)
Other versions
EP1074369B1 (de
Inventor
Rober Meuwly
Henri Hinc
Hervé Mousty
Marcel Tornare
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Conception et Developpement Michelin SA
Original Assignee
Michelin Recherche et Technique SA Switzerland
Conception et Developpement Michelin SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of EP1074369A1 publication Critical patent/EP1074369A1/de
Application granted granted Critical
Publication of EP1074369B1 publication Critical patent/EP1074369B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/20—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/10—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation for articles of indefinite length
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0014—Shaping of the substrate, e.g. by moulding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • Y10T156/1043—Subsequent to assembly

Definitions

  • the present invention relates to methods of manufacturing composite parts, in particular in the case of parts with complex shapes. It relates more particularly to parts composites very highly mechanically stressed.
  • a method of manufacturing composite parts consists in compression molding a paste under high pressures then complete polymerization before demolding.
  • the dough was previously prepared, and comprises a mixture of resin and short fibers. This process is very widely used due to its ability to manufacture parts with complex shapes and its high productivity.
  • the compression molding process is incompatible with the use of long reinforcing fibers. For this reason, we cannot consider using this process to produce the most mechanically stressed parts
  • the objective of the invention is to provide a method for manufacturing parts composites without degradation of the maximum possible reinforcing effect depending on the fibers which is applicable to a wide variety of shapes, including radii of curvature very small.
  • Another objective is to be able to introduce the components of the composite part into an open mold, like a tire mold, which in practice excludes injection techniques.
  • the invention aims to propose a manufacturing technique which meets the objectives mentioned above and which lends itself to the mechanization and fast rates sought for industrial manufacturing.
  • the process is more specifically intended for the use of fibers of infinite length.
  • a spun yarn generally comprising a large number (of the order of a hundred) of filaments elementary with a diameter of a few microns, these filaments being all side by side, therefore substantially parallel to each other, with a few overlaps. If it is indeed impossible to guarantee absolutely perfect storage of the filaments in parallel, we want to indicate by the expression "substantially parallel to a plane" that it is not a cable or a braid and that the filaments are arranged parallel to the geometric precision of the arrangement by.
  • the preferred reinforcement direction is for example the direction of tensile stresses in the workpiece. But we can also start with a ribbon or a fabric not only having fibers oriented parallel to one another, called warp yarns, which will be oriented in said preferred direction, and also containing other fibers, constituting for example weft threads, whatever the density.
  • the fiber impregnation step is not in itself specific to the present invention, man can easily select any suitable method, the impregnation can precede or follow the fiber arrangement phase parallel to a plane.
  • Arranging the fibers parallel to a plane aims that, at the latest while we start the polymerization of the resin, the reinforcing fibers are properly arranged to that they are, in the final composite part, judiciously arranged to provide fully the strengthening effect.
  • precomposite is understood to mean a material the resin of which is prepolymerized until it forms a solid medium (so-called gelation stage or beyond), so that the precomposite has a sufficient cohesion to be able to be installed in an open mold, with the stresses mechanical that this implies, without risking a "spin" of the fibers during which the rate of resin of the preform would decrease in an uncontrolled manner.
  • the objective of the prepolymerization is therefore to reach a minimum level of polymerization making it possible to avoid any flow of resin during a subsequent treatment thereof (in fact, a treatment of the composite or of the article in which it will be incorporated) under the action of temperature, or even under the action of pressure.
  • the objective of the prepolymerization is also to reach a minimum level of polymerization allowing the precomposite to resist buckling of its fibers during a bending as imposed by the application step on a non-planar support.
  • the polymerization initiated by ionizing radiation not only achieves this stage, but also makes it possible to stop the polymerization process by ceasing to emit said radiation. Indeed, the objective of the prepolymerization is still not to exceed a level maximum polymerization, allowing the bonding of the precomposite either on itself or on rubber as will be explained in detail below.
  • the prepolymerization as proposed associated with an implementation of the material by stratification in sufficiently thin layers, to reconstitute a shape block and any thickness, compared to a monolithic material prepared with the same resin and the same fibers in identical density, prepared for example by pultrusion.
  • ionizing radiation it is proposed to use radiation in the spectrum ranging from 300 nm to 450 nm, or an accelerated electron beam.
  • stresses are exerted on said precomposite sections in order to force them to intimately follow said shape of the support.
  • the surface of the support against which the sections are stacked is developable; it's easier to make them intimately marry said area.
  • the deformation stresses are maintained on said sections of precomposite at least until the start of the heat treatment step.
  • the start of polymerization is advantageously carried out in a layer of thickness "e” such that ⁇ e ⁇ is smaller than ⁇ r ⁇ divided by 20.
  • the beginning of the polymerization is carried out in a layer of thickness "e” such that ⁇ e ⁇ is smaller than ⁇ r ⁇ divided by 150.
  • an impregnation device 20 comprising a reservoir 21 containing a composition based on a curable resin and a photoinitiator suitable for the radiation by which said composition will be treated.
  • the device impregnation 20 includes an impregnation chamber 22.
  • a prepreg 12 which results therefrom is introduced into a prepolymerization device 30, in which the prepreg 12 is prepolymerized with ionizing radiation, the treatment being carried out away from oxygen.
  • the radiation 31 to which the composition is exposed its wavelength is typically less than 450 nanometers, preferably between 300 nm and 450 nm.
  • rollers 40 drive the precomposite 13 obtained in the direction of arrow F.
  • a shears 50 makes it possible to take sections 14 from the precomposite manufactured continuously, to implement them as explained below.
  • the prepolymerization level must be high enough to allow the stacking of sections 14 on the desired support without causing the fibers 11 to buckle inside the curvature of the deformed section 14, and to prevent the resin-based composition from becoming spreads outside the precomposite during deformation, and also during treatment subsequent thermal under pressure.
  • This level of prepolymerization must however be low enough for further polymerization of a stack of several sections of this precomposite under the combined effect of temperature and pressure creates connections across the interface between two adjacent precomposite sections, in order to obtain a composite material object with excellent mechanical properties, particularly in bending and in shear.
  • the step of exposure to radiation ionizing is stopped after the index D consisting of the Shore D hardness of the divided precomposite by the Shore D hardness of the final composite has reached a value of the order of 0.5 and before said index D has reached a value of the order of 0.7.
  • T g of the composition of the precomposite It is also possible to experimentally control the level of prepolymerization by means of an analysis of the glass transition temperature T g of the composition of the precomposite.
  • T gpr being the glass transition temperature of the composition of the precomposite
  • T gf being the glass transition temperature of the composition of the final composite
  • the exposure to ionizing radiation is stopped after the glass transition temperature T g of the composition of the precomposite has reached a value of the order of 40 ° C. and before the glass transition temperature T g of the composition of the precomposite has reached a value of the order of 130 ° C.
  • the level of prepolymerization of the precomposite is such that we are beyond the gel point of the resin.
  • the level of prepolymerization desired is achieved by adapting for example the treatment time to ionizing radiation (running speed imposed by the rollers 40, length of the prepolymerization device 30).
  • Figure 3 shows schematically the final step.
  • a counter-mold 62 is brought over the support 61 coated with a stack 16 of sections 14 of precomposite.
  • a final molding is carried out under pressure, for example of the order of 10 bars.
  • the temperature during the pressure molding is preferably higher than the glass transition temperature T g of the composition of the precomposite.
  • a suitable treatment temperature is of the order of at least 150 ° C.
  • the final properties of the material are not only and not even mainly due to said prepolymerization. They also largely result from the heat treatment during this final molding step, which ensures excellent bonding of the sections previously stacked on each other.
  • the control of the degree of prepolymerization is not carried out by thermal, it is possible to adjust the viscosity of the composition during the impregnation step fibers by a moderate rise in the temperature of said composition. For example, we can heat up to around 80 ° C, without any appreciable effect on the stability of the resin. This allows a much better impregnation of the fibers. We can thus have a adjustment parameter of the impregnation phase independent of the step parameters of the process.
  • the resin can be chosen in the group consisting of vinyl ester resins and unsaturated polyester resins, or alternatively may be an epoxy resin.
  • the reinforcing fibers let’s mention that they can be chosen from organic fibers such as high polyacrylic fibers tenacity or oxidized polyacrylonitrile fibers, high tenacity polyvinyl alcohol fibers, aromatic polyamide fibers or polyamide-imide fibers or polyimide fibers, chlorofibres, high tenacity polyester fibers or aromatic polyester fibers, fibers high tenacity polyethylene, high tenacity polypropylene fibers, cellulose fibers or rayon or high tenacity viscose, polyphenylene benzobisoxazole fibers, fibers polyethylene naphthenate, or they can be chosen from inorganic fibers such as glass fibers, carbon fibers, silica fibers, ceramic fibers (alumina, aluminosi
  • the following table gives comparative results on different samples 1 to 5, prepared at using different resins.
  • the samples prepared are parallelepipedic blocks 2 mm thick.
  • the reinforcing fibers are fibers of glass, of the type indicated.
  • "direct molding” means that we have prepared an equivalent monolith without any stratification; fibers parallel to each other are regularly distributed in the resin matrix. All samples have undergone final molding with pressure heat treatment.
  • Witness 1 was prepared with a prepreg of unidirectional fibers, commercially available under the name Prepreg Vicotex (reference BE M10 / 29.5% / 25x2400 - Glass strip P122 EPOXY 60 mm), and consisting of unidirectional glass fibers embedded in an epoxy resin, manufactured by Hexcel Composites S.A ..
  • witness 2 contains commercially available yarns under the name PPG 2001 300Tex, embedded in a commercially available resin under the name Atlac 590.
  • Witness 3 is obtained by stacking 10 sections of precomposite, the precomposite having been thermally prepolymerized. It contains the same glass fibers embedded in the same resin as control 2.
  • the composition comprises a photo polymerization initiator and radiation is included in the ultraviolet - visible spectrum.
  • a glass fiber is used.
  • All the samples of the invention are obtained by stacking 10 sections of 0.2mm thick precomposite, protected by two 50 micron nylon films.
  • the precomposite was prepolymerized by exposure for the number of seconds indicated under ultraviolet-visible radiation (Philips UV tube TLK 40W / 03) placed at a distance of 180 mm from the section.
  • the precomposite proves to be sufficiently transparent to radiation for the prepolymerization to be well homogeneous and for the provisional retention as set out above, in which the radiation treatment is carried out through an already prepolymerized section, to be effective.
  • the resins of controls 2 and 3 and of all the samples are all Vinylesters resins. (Epoxy Vinyl Ester Resins).
  • the supplier of ATLAC 590 resin is DSM - BASF Structural Resins. Note in passing that, as a variant of what was said in the previous paragraph, we can adjust the viscosity of said composition by adding a monomer copolymerizable with it resin and varying the proportion. For example the monomer which is varied proportion is styrene.
  • the photoinitiator is bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819 photoinitiator).
  • the supplier of the resin ⁇ Heltron 970 ⁇ is Ashland Chemical.
  • the supplier of resins ⁇ RD903 ⁇ and ⁇ RD904 ⁇ is UCB Chemicals.
  • the resin supplier ⁇ Derakane 470-36S ⁇ is Dow.
  • witnesses 1 and 2 illustrate the best performance that can be expected from a monolith properly prepared.
  • the mechanical performances of the samples are illustrated by the value of the Young's Modulus, by the maximum stress at rupture of the sample in bending test (Standard Afnor T57-302), and by the maximum shear stress at break (Standard Afnor T57-303), this latter property notably making it possible to clearly highlight the quality of the connection between the strata of control 3 and of the sample according to the invention.
  • the invention allows to substantially find the properties of witness 2, which is a monolith directly comparable.
  • the mechanical properties of the material are the same, as the sections of precomposite have been distorted or not.
  • the following table illustrates the partial polymerization treatment. It gives a qualitative description of the precomposite obtained for different values of the time of treatment with ultraviolet radiation.
  • the samples concerned contain PPG 300 Tex glass fibers at 70% by weight, embedded in an Atlac 590 resin with 2% Irgacure 819 Photoinitiator.
  • the precomposite is prepared in a 0.25 mm thick layer 30 mm wide, the glass fibers being unidirectional. The layer is protected on the surface by a nylon film 50 microns thick for irradiation. The irradiation is ensured by 2 Philips TLK 40W / 03 UV tubes placed at a distance of 180 mm from the layer to be treated. A stack of 15 sections of 30 mm precomposite is then formed.
  • the resistance to buckling is evaluated by manual winding of a sample oriented in the direction of the fibers on a cylinder with a radius of 30 mm. The resistance is evaluated at a pressure of 30 bars, at a temperature of 110 ° C. Shore D hardness is measured according to the standard already indicated. UV exposure time (sec) Surface appearance Shore D hardness Buckling resistance Pressure resistance 10 sticky 20 many buckling crushed composite, exuded resin 20 not poetic 35 buckling crushed composite 25 not poetic 45 little buckling composite not overwritten 27 not poetic 50 no buckling composite not overwritten 30 not poetic 65 no buckling composite not overwritten 40 not poetic 75 no buckling composite not overwritten 60 not poetic 80 no buckling composite not overwritten
  • the irradiation step is preferably limited in time as soon as the hardness Proper Shore D has been reached, the reader being referred to the explanations already provided.
  • the invention also extends to a laminated composite material of non-planar shape, comprising reinforcing fibers parallel to at least one preferred reinforcing direction, each fiber being entirely contained in a single layer, said fibers being embedded in a matrix based on a composition comprising a resin curable by ionizing radiation, in which each layer is less than 0.3 millimeter thick, in which the glass transition temperature T g of the matrix is greater than 150 ° C., and in which the Shore D hardness of the material is greater than 80.
  • each layer is non-planar and developable.
  • the material preferably such as the flexural modulus is greater than 30,000 MPa, the breaking stress in bending is greater than 1000 MPa, and the breaking stress in shear is greater than 70 MPa.
  • the invention makes it possible to obtain an intermediate product consisting essentially of a precomposite prepared in great length and in thickness of less than 0.3 millimeter, comprising reinforcing fibers parallel to at least one preferred reinforcing direction, said fibers being embedded in a matrix with base of a composition comprising a resin curable by ionizing radiation, in which the glass transition temperature T g of the matrix is between 40 ° C and 130 ° C, and in which the Shore D hardness of this precomposite is between 50 and 65, coated with a protective film opaque to ultraviolet radiation - visible. Thanks to the protective film, this intermediate product can be stored without significantly increasing the rate of prepolymerization. It can be used on another site and implemented according to the indications of the process of the invention.
  • the invention relates to a method of securing a composite material to rubber.
  • the method described makes it possible to produce a laminate in which said composite parts are intimately secured to rubber.
  • a layer of resorcinol formaldehyde latex adhesive RFL
  • said layer of RFL adhesive being dried without reaching a temperature higher than 100 ° C., that is to say without treatment thermal at high temperature, before receiving said rubber layer.
  • the invention therefore also extends to a material in which, between some of said layers at less, is interposed a layer 17 of composition based on sulfur vulcanizable elastomer.
  • a layer of adhesive is interposed resorcinol formaldehyde latex (RFL).
  • Figure 4 shows the support 61 first covered by two sections 14 of precomposite stacked, deformed and temporarily held by a layer 15 of the composition prepolymerized by ultraviolet radiation.
  • the two strata thus deposited and pre-stabilized spontaneously retain their C shape.
  • a layer 17 of a composition based on raw rubber is then deposited over the second section 14.
  • the rubber-based composition can marry without great difficulty the shape imposed on first layers of precomposite.
  • the final molding step illustrated in Figure 5, allows both the correct bonding of the sections 14 between them, the vulcanization of the rubber, the complete polymerization of the resin and the joining of rubber and resin.
  • a counter-mold 63 is brought over the support 61 coated with a stack 18 of precomposite sections 14 with interposition of a layer 17 rubber.
  • a final molding is carried out with heat treatment under pressure.

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  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Thermal Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Reinforced Plastic Materials (AREA)
  • Moulding By Coating Moulds (AREA)
  • Laminated Bodies (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Glass Compositions (AREA)
EP00115999A 1999-08-04 2000-07-26 Verfahren zur Herstellung von hochbeanspruchten Verbundteilen Expired - Lifetime EP1074369B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9910172 1999-08-04
FR9910172 1999-08-04

Publications (2)

Publication Number Publication Date
EP1074369A1 true EP1074369A1 (de) 2001-02-07
EP1074369B1 EP1074369B1 (de) 2005-10-05

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EP00115999A Expired - Lifetime EP1074369B1 (de) 1999-08-04 2000-07-26 Verfahren zur Herstellung von hochbeanspruchten Verbundteilen

Country Status (6)

Country Link
US (1) US6875297B1 (de)
EP (1) EP1074369B1 (de)
JP (1) JP4969717B2 (de)
AT (1) ATE305847T1 (de)
BR (1) BR0003354A (de)
DE (1) DE60022957T2 (de)

Cited By (38)

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GB2388069A (en) * 2002-03-08 2003-11-05 Structural Polymer Systems Ltd Manufacturing a preform moulding material
WO2004035300A1 (de) * 2002-10-12 2004-04-29 Menzolit Fibron Gmbh Reifung und schnelleindickung von smc/bmc- halbzeug durch bestrahlung mit elektromagnetischen strahlen
WO2004058909A1 (fr) * 2002-12-27 2004-07-15 Conception Et Developpement Michelin S.A. Composition adhesive pour le collage direct d'un composite polyester ou vinylester pregelifie a du caoutchouc cru
WO2004113058A1 (en) * 2003-06-25 2004-12-29 Joseph Steven Egan Method of construction of moulded products
RU2317205C2 (ru) * 2003-06-25 2008-02-20 Джозеф Стивен ЭГАН Способ изготовления формованных изделий
WO2012032000A1 (fr) 2010-09-09 2012-03-15 Societe De Technologie Michelin Roue elastique non pneumatique multietages
US8585947B2 (en) 2006-01-27 2013-11-19 Michelin Recherche Et Technique S.A. Process for manufacturing a composite ring
WO2013182598A1 (fr) 2012-06-07 2013-12-12 Compagnie Generale Des Etablissements Michelin Tringle pliable pour pneumatique
WO2013182597A1 (fr) 2012-06-07 2013-12-12 Compagnie Generale Des Etablissements Michelin Tringle hybride élastique pour pneumatique
WO2013182599A1 (fr) 2012-06-07 2013-12-12 Compagnie Generale Des Etablissements Michelin Tringle hybride allégée pour pneumatique
DE10233300B4 (de) * 2002-07-22 2014-09-11 Dieffenbacher GmbH Maschinen- und Anlagenbau Verfahren und Anlage zur Herstellung von faserverstärkten Formteilen
WO2015090973A1 (fr) 2013-12-19 2015-06-25 Compagnie Generale Des Etablissements Michelin Renfort multi-composite pour pneumatique
WO2015165777A1 (fr) 2014-04-29 2015-11-05 Compagnie Generale Des Etablissements Michelin Renfort plat multi-composite
CN105408536A (zh) * 2013-08-01 2016-03-16 米其林集团总公司 经改进的cvr(玻璃树脂复合材料)单丝
WO2016116457A1 (fr) 2015-01-21 2016-07-28 Compagnie Generale Des Etablissements Michelin Renfort multi-composite verre-résine à propriétés améliorées
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WO2016189126A1 (fr) 2015-05-28 2016-12-01 Compagnie Generale Des Etablissements Michelin Renfort plat multi-composite
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WO2020109723A1 (fr) 2018-11-30 2020-06-04 Compagnie Generale Des Etablissements Michelin Collage d'un monobrin en composite verre-résine à une matrice thermoplastique
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FR3089219A1 (fr) 2018-11-30 2020-06-05 Compagnie Generale Des Etablissements Michelin Matériau multi-composite à base de composite verre-résine
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FR3089994A1 (fr) 2018-12-18 2020-06-19 Compagnie Generale Des Etablissements Michelin Composition de résine comprenant un agent de réticulation spécifique
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FR3117481A1 (fr) 2020-12-16 2022-06-17 Compagnie Generale Des Etablissements Michelin Utilisation de fibres composite verre-resine pour le renforcement du beton
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WO2023242268A1 (fr) 2022-06-15 2023-12-21 Compagnie Generale Des Etablissements Michelin Utilisation de fibres composite carbone-resine pour le renforcement du beton
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FR3009226B1 (fr) * 2013-08-01 2016-01-01 Michelin & Cie Procede de fabrication d’un monobrin en composite verre-resine
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US7473472B2 (en) 2002-12-27 2009-01-06 Conception Et Developpment Michelin S.A. Adhesive composition for the direct joining of a pre-gelled polyester or vinyl ester to raw rubber
WO2004113058A1 (en) * 2003-06-25 2004-12-29 Joseph Steven Egan Method of construction of moulded products
RU2317205C2 (ru) * 2003-06-25 2008-02-20 Джозеф Стивен ЭГАН Способ изготовления формованных изделий
US8585947B2 (en) 2006-01-27 2013-11-19 Michelin Recherche Et Technique S.A. Process for manufacturing a composite ring
WO2012032000A1 (fr) 2010-09-09 2012-03-15 Societe De Technologie Michelin Roue elastique non pneumatique multietages
WO2013182598A1 (fr) 2012-06-07 2013-12-12 Compagnie Generale Des Etablissements Michelin Tringle pliable pour pneumatique
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US6875297B1 (en) 2005-04-05
JP4969717B2 (ja) 2012-07-04
BR0003354A (pt) 2001-04-10
DE60022957D1 (de) 2006-02-16
DE60022957T2 (de) 2006-07-20
ATE305847T1 (de) 2005-10-15
EP1074369B1 (de) 2005-10-05

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